1. Field of the Invention
The present invention relates to high performance wire and cable resins and to hot melt adhesives containing a silyl grafted ethylene copolymer having particularly low levels of a glycidyl acrylate comonomer.
2. Description of the Related Art
U.S. Pat. Nos. 5,389,728 and 5,484,847 describe the preparation and use of moisture curable, melt processible, graft copolymers which are obtained by reacting certain ethylene copolymers having copolymerized therewith a glycidyl containing comonomer(s) which is then further reacted with a particular grafting agent selected from N-tert-butylaminopropyl trimethoxysilane. This particular class of grafted copolymers was described as sufficiently stable for co-extrudable hot melt adhesive use. Wire and cable applications were also mentioned for this particular class. The above patent disclosures also clearly described certain substituted aminopropyl trimethoxysilanes grafted ethylene copolymers (ethylene/alkyl acrylate/glycidyl methacrylate as the direct copolymer) which were particularly unsuitable for hot melt adhesive use because of their thermal instability under hot melt adhesive use conditions. Included among the list of particularly unsuitable silanes to be utilized as a grafting reagent was N-cyclohexylaminopropyl trimethoxysilane as well as numerous others. Comparative example 2 in U.S. Pat. No. 5,389,728 clearly shows the unsuitability of a copolymer having ethylene, an alkyl acrylate and a glycidyl termonomer grafted with N-cyclohexylaminopropyl trimethoxysilane. The only suitable N-alkylaminopropyl trimethoxysilane for hot melt adhesive use was the patented t-butyl derivative. Other comparative unsuitable examples were also described.
On the other hand, and with respect to vinyl acetate containing copolymers, U.S. Pat. No. 5,484,847 did not disclose any specific comparative examples showing other N-substituted aminopropyl trimethoxysilanes and only specifically disclosed an ethylene/vinyl acetate/glycidyl methacrylate copolymer containing 11.1 wt. % EVA and 7.4 wt. % glycidyl methacrylate with N-tert-butylaminopropyl trimethoxysilane grafted thereto. This patent disclosure did not teach anything about the use or potential use of other N-substituted aminopropyl trimethoxysilanes as grafting reagents with vinyl acetate containing ethylene copolymers. All comparative examples and/or teachings with respect to any reagent other than N-tert-butylaminopropyl trimethoxysilanes were directed to the alkyl acrylate containing copolymers.
Both patent disclosures discussed above expressly or implicitly teach away from the use or potential use of ethylene copolymers having an alkyl acrylate or a vinyl acetate as a comonomer along with a glycidyl containing comonomer which is subsequently grafted with an aminosilane other than the specific t-butylaminopropyl trimethoxysilane.
Furthermore, the above patent disclosures suggest that at lower percentages of glycidyl moiety in the disclosed compositions (equal to or less than 6 percent) grafting catalysts are required to speed up the grafting reaction.
In view of the above, there is a need to develop additional copolymers which provide good performance in hot melt adhesives as well as wire and cable applications which continue to demand reliable physical properties at extreme temperatures or wide temperature variations and which can be readily made in an extruder. In addition, prior art thermoset resins generally require continuous vulcanization (CV) tubes and/or radiation equipment to provide high performance thermoset properties and known vinyl silane moisture curable systems typically require peroxide, catalyst and high graft temperatures which can lead to undesired side crosslinking reactions and an increase in compound viscosity.
The present inventors have discovered a thermally stable grafted terpolymer having a glycidyl moiety which contains an N-cyclohexyl-aminopropyl trimethoxysilane or other N-alkyl- or N-arylalkylaminopropyl trimethoxysilanes which were formerly thought to be unsuitable and which do not require a CV tube, peroxide, extruder catalyst addition or high graft temperatures. It has been discovered that because of a specific low range of glycidyl monomer in the present invention, thermal stability is achieved for hot melt adhesive compositions having the claimed grafted copolymers therein. It has also been surprisingly found that catalysts are unnecessary to effect the grafting reaction at these lower percentages of glycidyl monomer and that moisture-curing catalysts are also unnecessary.
The present inventors have also found that the relative composition of the direct copolymer, wherein one of the monomers is vinyl acetate, affects the suitability of a grafted copolymer based thereon for wire and cable applications. It has also been found that an ethylene vinyl acetate copolymer having a narrow, specific range of glycidyl comonomer which is subsequently grafted in an extruder with an N-substituted aminopropyl trimethoxysilane (excluding N-t-butyl) and subsequently formed into a coating for a wire or cable (or material suitable for forming a coating for a wire and cable) provides a particularly effective wire and cable coating with good moisture curing thermoset properties, thus, further providing effective wire and cable products.
Thus the present invention provides a thermally-stable, grafted copolymer E/X/Y-(G) composition comprising monomers E, X, and Y in random order and grafting reagent G, wherein:
E is ethylene;
X comprises from 8 to 70 weight percent relative to the total weight of E/X/Y and is selected from the group consisting of a C1 to C8 alkyl acrylate, a C1 to C8 alkyl methacrylate, and vinyl acetate;
Y comprises about 1 to 4 weight percent relative to the total weight of E/X/Y of a glycidyl containing monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether; and
G comprises from 15 to 150 percent of a stoichiometric amount with respect to the weight of the glycidyl moiety, of a secondary aminosilane compound of the formula
Rxe2x80x94N(H)xe2x80x94Rxe2x80x2xe2x80x94Si(ORxe2x80x3)3
wherein Rxe2x80x2 is a C1 to C6 alkylene group, Rxe2x80x3 is a C1 to C6 alkyl group, and R is selected from
a) a secondary radical of the formula xe2x80x94CHR1R2 wherein R1 and R2 are independently selected from C1 to C6 alkyl or C1-C6 arylalkyl and wherein R1 and R2 may be joined to form a C5 to C9 cycloaliphatic ring; or
b) a primary radical of the formula xe2x80x94CH2R3 wherein R3 is selected from (i) a C3 to C12 alkyl group, wherein, in the case of a C3 to C6 alkyl group, said alkyl moiety is branched, or (ii) a (C1 to C12 alkyl)-aryl group, wherein R1, R2, and R3 may be unsubstituted or substituted with substituents selected from C1-C4 alkyl.
Preferably the X comprises about 8 to 50 weight percent and most preferably about 8 to 46 weight percent of the E/X/Y copolymer and the Y can be from about 0.5 to 9 weight percent, and preferably about 1 to 4 weight percent of the E/X/Y copolymer.
The present invention also comprises a grafted copolymer having zero mole percent X corresponding to the formula E/Y-(G) as illustrated in Example 5 (grafted ethylene/GMA). As such the present invention provides a thermally-stable, grafted copolymer E/X/Y-(G) composition comprising monomers E, X, and Y in random order and grafting reagent G, wherein:
E is ethylene;
X comprises from 0 to 70 weight percent relative to the total weight of E/X/Y and is selected from the group consisting of a C1 to C8 alkyl acrylate, a C1 to C8 alkyl methacrylate, and vinyl acetate;
Y comprises about 1 to 4 weight percent relative to the total weight of E/X/Y of a glycidyl containing monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether; and
G comprises from 15 to 150 percent of a stoichiometric amount with respect to the weight of the glycidyl moiety, of a secondary aminosilane compound of the formula
Rxe2x80x94N(H)xe2x80x94Rxe2x80x2xe2x80x94Si(ORxe2x80x3)3
wherein Rxe2x80x2 is a C1 to C6 alkylene group, Rxe2x80x3 is a C1 to C6 alkyl group, and R is selected from
a) a secondary radical of the formula xe2x80x94CHR1R2 wherein R1 and R2 are independently selected from C1 to C6 alkyl or C1-C6 arylalkyl and wherein R1 and R2 may be joined to form a C5 to C9 cycloaliphatic ring; or
b) a primary radical of the formula xe2x80x94CH2R3 wherein R3 is selected from (i) a C3 to C12 alkyl group, wherein, in the case of a C3 to C6 alkyl group, said alkyl moiety is branched, or (ii) a (C1 to C12 alkyl)-aryl group, wherein R1, R2, and R3 may be unsubstituted or substituted with substituents selected from C1-C4 alkyl.
The grafted polymeric compounds according to the instant invention are thermally stable and have a melt index ranging from 1 to 2000. The melt index is preferably 1 to 60 for wire and cable applications and 50 to 2000 for hot melt adhesives.
The present invention also comprises thermally-stable, melt-processible, moisture-curable, graft copolymer composition which comprises the reaction products of a direct ethylene copolymer containing epoxide groups and a grafting compound, wherein said grafting compound is a secondary aminosilane compound of the formula
Rxe2x80x94N(H)xe2x80x94Rxe2x80x2xe2x80x94Si(ORxe2x80x3)3
wherein R contains up to 12 carbons, Rxe2x80x2 is a C1 to C6 alkylene group, Rxe2x80x3 is a C1 to C6 alkyl group, and the direct ethylene copolymer is derived from monomers comprising:
(a) ethylene;
(b) 8 to 70 weight percent of C1 to C8 alkyl acrylate or methacrylate or vinyl acetate;
(c) 1 to 4 weight percent of a glycidyl containing monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether.
The present invention also relates to hot melt adhesive compositions or wire and cable compositions containing or comprising said grafted copolymer compositions and to hot melt adhesive compositions and/or wires and cables which contain the post-extrusion, post-hydrolyzed crosslinked versions of said polymer compositions.
The invention herein also relates to a method for coating a wire comprising the steps of:
(a) extruding a mixture of a direct ethylene copolymer composition containing epoxide groups and a grafting compound around a wire, wherein said direct ethylene copolymer is derived from monomers comprising:
(i) ethylene;
(ii) 8 to 70 weight percent of C1 to C8 alkyl acrylate or methacrylate or vinyl acetate;
(iii) 1 to 4 weight percent of a glycidyl containing monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether, and
xe2x80x83said grafting compound comprises about 15 to 150 weight percent of a stoichiometric amount with respect to the weight of the glycidyl moiety of a secondary aminosilane of the formula
Rxe2x80x94N(H)xe2x80x94Rxe2x80x2xe2x80x94Si(ORxe2x80x3)3
wherein Rxe2x80x2 is a C1 to C6 alkylene group, Rxe2x80x3 is a C1 to C6 alkyl group, and R is selected from
(i) a secondary radical of the formula xe2x80x94CHR1R2 wherein R1 and R2 are independently selected from C1 to C6 alkyl or C1-C6 arylalkyl and wherein R1 and R2 may be joined to form a C5 to C9 cycloaliphatic ring; or
(ii) a primary radical of the formula xe2x80x94CH2R3 wherein R3 is selected from (i) a C3 to C12 alkyl group, wherein, in the case of a C3 to C6 alkyl group, said alkyl moiety is branched, or (ii) a (C1 to C12 alkyl)-aryl group, wherein R1, R2, and R3 may be unsubstituted or substituted with substituents selected from C1-C4 alkyl; and
(b) curing the coating on the wire by contacting the coated wire with water or air having a relative humidity of greater than 50%.
The invention also relates to method to improve the thermal stability of N-(substituted) aminopropyl trimethoxysilane grafted ethylene copolymers comprising:
(a) selecting a direct ethylene copolymer derived from monomers comprising:
(i) ethylene;
(ii) 8 to 70 weight percent of C1 to C8 alkyl acrylate or methacrylate or vinyl acetate;
(iii) 1 to 4 weight percent of a glycidyl containing monomer selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and glycidyl vinyl ether, and
(b) contacting the copolymer of a with a grafting compound comprising about 15 to 150 weight percent of a stoichiometric amount with respect to the weight of the glycidyl moiety of a secondary aminosilane of the formula
Rxe2x80x94N(H)xe2x80x94CH2CH2CH2xe2x80x94Si(OCH3)3
wherein R is selected from
(i) a secondary radical of the formula xe2x80x94CHR1R2 wherein R1 and R2 are independently selected from C1 to C6 alkyl or C1-C6 arylalkyl and wherein R1 and R2 may be joined to form a C5 to C9 cycloaliphatic ring; or
(ii) a primary radical of the formula xe2x80x94CH2R3 wherein R3 is selected from (i) a C3 to C12 alkyl group, wherein, in the case of a C3 to C6 alkyl group, said alkyl moiety is branched, or (ii) a (C1 to C12 alkyl)-aryl group, wherein R1, R2, and R3 may be unsubstituted or substituted with substituents selected from C1-C4 alkyl,
to form a thermally-stable, N-(substituted) aminopropyl trimethoxysilane grafted ethylene copolymer.
Definitions
The term xe2x80x9cdirect copolymerxe2x80x9d refers to a polymeric chain made from the respective monomeric units and serves as the base polymer for the xe2x80x9cgrafted copolymerxe2x80x9d which includes a grafting reagent (or portion thereof) covalently bonded to the base polymer.
The term xe2x80x9cglycidylxe2x80x9d refers to a group derived from 2,3-epoxy-1-propanyl and a glycidyl monomer is an epoxy containing monomer.
The term xe2x80x9cthermally stablexe2x80x9d means that the grafted copolymer of the invention does not undesirably crosslink (or decompose) at the temperatures necessary to form or use the particular grafted direct copolymer without also negatively affecting the stability of the base direct copolymer or of the grafted polymer to the extent that such polymer cannot be satisfactorily used as a hot melt adhesive or as a wire and cable composition. The temperatures referred to above may vary depending upon the non-ethylene components in the direct copolymer (for example vinyl acetate versus alkyl acrylates) and also depends upon the nature of the silane grafting reagent.
For suitability as a hot melt adhesive, the composition needs to be thermally stable in a hot melt container over an extended period of time at a temperature of, for example, 135 degrees Centigrade. The grafted polymers of this invention are thermally stable under these conditions. The vinyl acetate containing polymers are suitable as wire and cable compositions and are stable under the conditions necessary to form the compositions (in an extruder) for wire and cable applications.
The compositions of the invention are high performance polymeric compositions suitable for wire and cable and hot melt adhesive use. The recited compositions do not require special equipment (i.e. CV tubes) or peroxides, extruder catalysts or high graft temperatures to achieve significant thermoset properties suitable for wire and cable compositions and for hot melt adhesive compositions.
The inventors have surprisingly found that lower levels of GMA or glycidyl moiety in the direct copolymer described herein coupled with the particular type of grafting material influences the temperature at which grafting occurs (e.g. grafting can occur at lower temperatures) and influences the variability of the grafting reaction in terms of graft level (e.g. provides more consistent-less variable-grafting levels). Grafting at lower temperatures is particularly suitable for wire and cable compositions because crosslinking side reactions are minimized.
The compositions of the invention include thermally stable hot melt adhesive compositions and wire and cable compositions. The thermally stable hot melt adhesive compositions are N-substituted aminopropyl trimethoxysilane grafted ethylene alkyl acrylate or alkyl methacrylate copolymers also having as a third comonomer a low weight percentage of an epoxy containing monomer beta to the nitrogen on the grafting agent. The wire and cable compositions are N-substituted aminopropyl trimethoxysilane grafted ethylene vinyl acetate copolymers also having as a third comonomer a low weight percentage of a epoxy containing monomer beta to the nitrogen on the grafting agent. Secondary aminosilane compounds based on triethoxysilane composition comprise the invention also.
The compositions of the invention are thermally-stable, graft copolymers which are the reaction products of a direct ethylene copolymer containing epoxide groups and a grafting compound which is a secondary aminosilane compound of the general formula Rxe2x80x94N(H)xe2x80x94Rxe2x80x2xe2x80x94Si(ORxe2x80x3)3 wherein Rxe2x80x2 is a C1 to C6 alkylene group, Rxe2x80x3 is a C1 to C6 alkyl group, and preferably of the formula Rxe2x80x94N(H)xe2x80x94CH2CH2CH2xe2x80x94Si(OCH3)3 wherein R is selected from
a) a secondary radical of the formula xe2x80x94CHR1R2 wherein R1 and R2 are independently selected from C1 to C6 alkyl or C1-C6 arylalkyl and wherein R1 and R2 may be joined to form a C5 to C9 cycloaliphatic ring; or
c) a primary radical of the formula xe2x80x94CH2R3 wherein R3 is selected from (i) a C3 to C12 alkyl group, wherein, in the case of a C3 to C6 alkyl group, said alkyl moiety is branched, or (ii) a (C1 to C12 alkyl)-aryl group, wherein R1, R2, and R3 may be unsubstituted or substituted with substituents selected from C1-C4 alkyl.
The Direct Ethylene Copolymer
The direct copolymer (E/X/Y) derived by copolymerization of the monomeric the units of E, X, and Y in random order has a glycidyl monomer incorporated therein as defined above as the Y component in the percentage range of 0.5 to 9 wt. percent, preferably 1 to 4 weight percent. The glycidyl monomers are the glycidyl esters of acrylic and methacrylic acid and also glycidyl vinyl ether. Glycidyl methacrylate is especially preferred.
In order to provide thermal stability to the grafted copolymers of the invention, the percentage of glycidyl monomer in the terpolymer needs to be carefully controlled and should preferably be between 0.5 and 9 weight percent, with the preferred percentage when the grafting reagent is selected from N-cyclohexylaminopropyl trimethoxy silane being approximately 4 wt. % or less for hot melt adhesive application and 2 wt. % or less for wire and cable. Surprisingly, no catalyst is required for grafting or eventual moisture cure of a thermoset composition containing the grafted copolymer.
The X component of the direct ethylene copolymer is selected from C1 to C8 alkyl acrylates such as n-butyl acrylate or methacrylate and is present in a wt. percentage range relative to the other components in the direct copolymer of 8 to 70 weight percent, preferably 8 to 50 weight percent, most preferably 8 to 46 weight percent. The X component may also be selected from a vinyl acetate moiety in the same weight range.
These copolymers containing the E/X/Y components in the weight percentages listed above are generally prepared by well-known methods of preparing such copolymers. These methods typically use a continuous stirred reactor at high temperatures and pressures, as described in U.S. Pat. Nos. 4,351,931 and 3,780,140. The melt index of the direct copolymers used as precursors herein may have a melt index range of 1 to 2000.
Preparation of an E/X/Y terpolymer of ethylene n-butyl acrylate glycidyl methacrylate of weight % composition 66.75/28/5.25 as may be used in this invention typically involves polymerization in a stirred autoclave reactor above 20,000 psi and at reactor temperatures above 150xc2x0 C. Random monomer polymerization is initiated with peroxide free radicals. A telogen such as acetone is used to control molecular weight to the desired range. High and then low pressure separators are used to let down reactor pressure. Resin is isolated as pellets melt cut under water, dried, and packaged. The polymer described here is commercially available from DuPont as Elvaloy(copyright)AM resin, has a melt index of 12 g/10 min., crystalline melting point of 72xc2x0 C., and density of 0.94 g/cm3. Stress strain properties by ASTM D638 with a 2 inch/min. pull rate are 750 psi (5.2 mPa) tensile strength, 950% elongation at break, and 73 Shore A durometer hardness.
Preparation of an E/X/Y terpolymer of ethylene vinyl acetate glycidyl methacrylate of weight % composition 66.75/32/2 as may be used in this invention is carried out by polymerization in a stirred autoclave at 27,000 psi pressure, 168xc2x0 C. reactor temperature, and peroxide free radical initiation. An acetone telogen is used to control molecular weight to provide resin with melt index in the range of 3-50 g/10 min. isolated after pressure let down, melt pelletization, and drying.
The direct copolymers utilized in this invention having a vinyl acetate component have a Melt Index range of between 1 and 60 g/10 min. and are suitable for wire and cable applications. The resulting grafted copolymers prepared from these direct copolymers should have a MI range that is similar to the precursor direct copolymer. No major change in MI properties should generally occur upon grafting; the MI of the grafted polymer is usually not more than 20% different than the precursor copolymer.
The Grafting Reagent
As described above, the grafting reagent is selected from an N-substituted aminoalkyl trialkoxysilane which after grafting and upon moisture cure provides good thermoset and/or controlled crosslinking for the hot melt adhesive or the wire and cable composition. Generally these reagents are commercially available or made from commercially available precursors.
The suitable aminosilanes are selected from a compound of the formula Rxe2x80x94N(H)xe2x80x94Rxe2x80x2xe2x80x94Si(ORxe2x80x3)3 
wherein Rxe2x80x2 is a C1 to C6 alkylene group, Rxe2x80x3 is a C1 to C6 alkyl group, and R is selected from
a) a secondary radical of the formula xe2x80x94CHR1R2 wherein R1 and R2 are independently selected from C1 to C6 alkyl or C1-C6 arylalkyl and wherein R1 and R2 may be joined to form a C5 to C9 cycloaliphatic ring; or
b) a primary radical of the formula xe2x80x94CH2R3 wherein R3 is selected from (i) a C3 to C12 alkyl group, wherein, in the case of a C3 to C6 alkyl group, said alkyl moiety is branched, or (ii) a (C1 to C12 alkyl)-aryl group, wherein R1, R2, and R3 may be unsubstituted or substituted with substituents selected from C1 to C4 alkyl.
The secondary radicals are selected from, for example, isopropyl, isobutyl or cyclohexyl or C1 to C4 alkyl substituted versions thereof and are also selected from an arylalkyl such as benzyl, phenylethyl and the like. The primary radicals are selected from moieties such as isobutyl, xe2x80x94CH2CH(CH3)2 or higher homologs such as, xe2x80x94CH2(C4H9 to C11H23) and also include a C1 to C12 alkyl substituted arly or simiolar arlyalkyl, collectively a (C1 to C12 alkyl)-aryl group. The preferred aminosilane is Rxe2x80x94N(H)xe2x80x94CH2CH2CH2xe2x80x94Si(OCH3)3 where R is cyclohexyl.
The Resulting Grafted Ethylene Copolymer
The grafted ethylene copolymer of the invention herein results from the reaction product(s) of the direct copolymer and the grafting reagent described above. The glycidyl group reacts with the secondary amine (amino) group of the aminosilane. The stoichiometric amount of the secondary amino silane relative to the glycidyl moiety can vary considerably from 15 to 150 percent, based on weight. The skilled artisan can vary this according to the degree of crosslinking desired in the post-extruded, post-hydrolyzed product. The resulting crosslinking leads to high heat resistance, oil resistance, mechanical strength, good abrasion as well as cut resistance etc.
In general, the grafting reaction occurs by contacting the direct copolymer and the aminosilane in, e.g., a high shear melt mixer such as an extruder equipped with a suitable mixing screw or other high shear mixers such as a Banbury, Brabender or Haake mixer, though any suitable mixer is contemplated. Melt temperatures above 110xc2x0 C. are used to allow sufficiently rapid reaction without increasing the possibility of undesirable side reactions. Stearic acid and triphenylphosphine may be further or additionally added to the reaction system to catalyze the reaction although, as indicated above, they are not required or necessary.
Generally, reaction temperatures above 220xc2x0 C. are not suitable when vinyl acetate is in the polymer because of potential polymer degradation. No solvent is generally used and hold up times required for complete reaction are typically about 1 to 10 minutes depending upon the temperature, shear and/or catalyst system if present. While close to stoichiometric amounts of aminosilane and glycidyl moiety are most suitable, an aminosilane/glycidyl ratio of from 0.15/1 to 1.5/1 can be used. The process of preparation is that as described in the examples. In contrast to the use of t-butyl derivatives as described in the prior art, high temperatures were not required to graft the aminosilane.
For wire and cable applications, the aminosilane is typically grafted to glycidyl methacrylate epoxy-containing polymers, such as ethylene vinyl acetate and ethylene n-butyl acrylate, by heating at 110 to 200xc2x0 C. in a high shear mixer such as a Banbury, Brabender, Haake, Buss co-kneader, or in a single or twin screw extruder for about 1 to 10 minutes, depending on the temperature. Grafting also takes place by compression or injection molding plaques containing the mixed compound of glycidyl methacrylate polymer and aminosilane. The reaction of N-cyclohexylaminopropyl trimethoxysilane with epoxy group of the glycidyl methacrylate moiety is rapid and complete at 150xc2x0 C. and even occurs at 110xc2x0 C. at reasonable rate.
In the absence of moisture, crosslinking does not take place and the grafted compound is re-shapeable. If sufficient moisture is present in the grafted compound, as may be introduced with a filler, scorch or pre-cure may occur and result in increased compound viscosity and difficulty in subsequent processing, such as extrusion on to wire. Use of dry fillers or pre-drying of compound ingredients minimizes potential scorch.
The grafted copolymers of the invention are suitable for use alone or in combination with other ingredients depending upon the final use/product. For example, they can be formulated with tackifiers or plasticizers or other excipients used in hot melt adhesives or in wire and cable compositions. These grafted copolymers may be used in neat form or blended with the stated excipients for either hot melt use or for wire and cable use. The grafted copolymers of the invention may further be processed and reshaped into the final configuration between 110xc2x0 C. and 170xc2x0 C. as long as moisture is avoided.
For hot melt adhesive use, the neat grafted copolymer can be utilized as a hot melt adhesive or it can be formulated. There are many possible formulations, but a typical formulation might contain about one third polymer, one third of a hydrocarbon wax (paraffin or microcrystalline), one third of a tackifier resin and ppm level of an antioxidant package (e.g. phenolic and phosphite). Sometimes only polymer, tackifying resin and antioxidant are included in the formulation. Tackifier resins commonly used are C5 and C9 hydrocarbon resins and rosin esters. Hot melt adhesives are normally produced in high shear batch mixers such as sigma blades, Banburys, Brabenders, Haake, etc. There are many uses for moisture-curable adhesives, including automotive gaskets, auto interior trim, auto head and tail lamps, furniture assembly including edge banding, bookbinding and general product assembly.
For wire and cable applications, the grafted copolymer is prepared by addition of aminosilane to the mixed compound in the wire coating extruder. Residence times of typically 3 to 5 minutes at temperatures of 150xc2x0 C. provide good conditions for grafting secondary aminosilanes inside the extruder during coating of the wire. No catalysts are needed for the grafting reaction. The coated wire is wound on a reel which then may be submerged in 75 to 80xc2x0 C. water for 8 to 24 hours to bring about moisture cure. Prior to cure some care in handling is required to avoid deformation. The water permeates through the coating to react with the trimethoxysilane groups on two separate polymers to form a Sixe2x80x94Oxe2x80x94Si crosslink bond with elimination of methanol.
For medium and high voltage power cable, an ethylene vinyl acetate- or n-butyl acrylate-glycidyl methacrylate semicon compound is extruded onto wire with grafting of aminosilane introduced in the wire line extruder. By the same procedure, an insulation compound of ethylene glycidyl methacrylate or other moisture curable polyethylene insulation is extruded with a second extruder over the semicon again with aminosilane introduced. And finally in a third extruder, a second outer semicon of ethylene vinyl acetate-glycidyl methacrylate and aminosilane is extruded and grafted in the extruder while wire coating. These three layers, all of which contain grafted aminosilane can then be simultaneously cured by submersion in warm water. This moisture cure technology is especially effective in power cables where semicon compounds contain relatively low filler levels and the PE insulation is unfilled so moisture crosslinking during grafting is minimal because of low moisture content in the compounds.
The same glycidyl epoxy/aminosilane technology provides moisture curable flame retardant non-halogen jackets and automotive primary wire. These compounds differ from power cable semicons in containing higher levels of mineral fillers so that greater care must be taken to assure dry compound ingredients to minimize pre-cure during grafting of the aminosilane. Any wire and cable compound (i.e., for use as semicon, insulation, and/or jacket) containing an epoxy group according to the instant invention can be grafted with an appropriate aminosilane under extruder conditions during wire line coating and subsequently be moisture cured with water to provide cables with attractive physical properties.
The resulting graft copolymers of this invention have a melt index (MI) of from 1 to 2,000. Higher melt index polymers are particularly suitable for hot melt adhesive use while the lower melt index polymers (e.g., vinyl acetate containing polymers) are suitable for wire and cable applications.
Moisture curing occurs by crosslinking of the direct polymer through the silane groups. Crosslinking during moisture cure causes increased strength and modulus. The crosslinking reaction on moisture treatment of the grafted copolymer can occur at room temperature and at 50% humidity or higher, but is accelerated at higher temperatures and higher relative humidity. Total immersion in warm water provides commercially attractive cure rates for coated wire.
Test Procedures
In the examples which follow, the preparation of the moisture curable ethylene graft copolymer is described. The rate of moisture cure is monitored by viscosity change and the thermal stability of the graft copolymers is determined.
Melt Index (MI) is determined using ASTM D-1238 (2160 g. load/190 deg. C. with values in units of g/10 min.).
Viscosity stability for adhesives was measured using a Brookfield viscometer at 135xc2x0 C. and a shear rate of 0.1 secxe2x88x921. The polymer is kept at this temperature in an open cup, and viscosity change continuously monitored. This temperature is a typical melt processing temperature for adhesives. For adhesives, long hold up times in the melt are desired. In the test, a viscosity increase of less than 50% over a period of eight hours is considered an indication of thermal stability and sufficient for adhesive use. Such a test is also indicative of stability at higher temperatures with shorter hold up times such as in an extrusion process where exposure to high temperature is generally in or over a several minute period.
The curability or ease at which the polymer crosslinks with moisture was determined in the following way. A 70 mil compression molded plaque was prepared using a press temperature of 120xc2x0 C. and a 5,000 pound load. The plaque was placed in a humidity chamber kept at 70xc2x0 C. and 95% relative humidity. After 24 hours, melt index tests are carried out. Low or no flow after this time indicates a good cure rate.
Viscosity stability for wire and cable was measured on the compound using a Mooney viscometer after 1+4 minutes at 100xc2x0 C. with the large rotor by ASTM D1646. Compounds were stored at 23xc2x0 C. in 50% relative humidity and Mooney viscosity (ML) increase measured over time.
Curability for wire and cable was determined by measurement of tensile properties by ASTM D412 of molded test plaques or coated wire. Volume resistivity, an important property for power cable semicons, was measured by ASTM D991. Volume resistivity for insulation material was measured by ASTM D257. Dielectric strength was measured by ASTM D149 in oil by increasing voltage at a rate of 500 volt/sec. Dielectric constant and dissipation factor were measured by ASTM D150.
For wire and cable samples, grafting of aminosilane was carried out either in compression molded 2 mm plaques heated 5 minutes at 150 or 180 (or 177)xc2x0 C. or in a wire line extruder at 60-150xc2x0 C. during wire coating. Moisture crosslinking through the silane groups of the grafted aminosilane was carried out by submersion of test plaques and coated wire in water at 80xc2x0 C. for 24 hours.